Time-related luminescence spectroscopic investigation of electron trapping and recombination in infrared stimulated luminescence

Infrared stimulated luminescence (ISL) occurred in CaS:Eu,Sm due to formation of luminescent centres Eu²⁺ and electron trapping centres Sm³⁺. The electron trapping centres Sm³⁺ became occupied (forming Sm²⁺ by trapping excited electrons) in photoluminescence (PL) excitation (PLX) process causing simultaneous ionization of luminescent centres Eu²⁺ (leaving Eu³⁺ by losing an electron or capturing a hole). In this paper, the electron trapping in PLX and the recombination in ISL were examined by the time-related PL and ISL spectra of CaS:Eu,Sm. The spectroscopic evidence confirmed that the ISL in CaS:Eu,Sm was produced due to recombination of de-trapped electrons and previously ionized luminescent centres (Eu³⁺). It was believed that the electron trapping occurred concurrently as occurrence of the PL of Eu²⁺ in PLX process. However, the recombination of de-trapped electrons and previously ionized luminescent centres took about 10 s or even more to occur after infrared irradiation. PACS 78.55.-m; 78.45.+h     

Excitation-energy transfer in infrared -stimulable CaS doubly doped with Eu and Sm

The photoluminescence emission (PLE) mapping and infrared-stimulated luminescence (ISL) spectra of CaS:Eu,Sm demonstrated that Eu is formed in Eu²⁺ as a luminescent centre, whereas Sm is formed in Sm³⁺ as an electron-trapping centre by replacing Ca²⁺ in the CaS host lattice. It was found that electron trapping occurred in the photoluminescence excitation (PLX) process. A series of concentrations of Eu with a fixed Sm concentration and a series of concentrations of Sm with a fixed Eu concentration in doubly doped CaS:Eu,Sm were studied by the time-related PLE of Eu²⁺ in the PLX process. According to the electronic energy level(s) of Eu²⁺ and Sm³⁺, excitation-energy transfer is realized by translocation of excited electrons from Eu²⁺ to Sm³⁺, causing simultaneous ionization of Eu²⁺ (leaving Eu³⁺) and capture of excited electrons at Sm³⁺ (forming Sm²⁺). ISL is then produced due to the energy released from recombination of de-trapped electrons from the occupied electron-trapping sites (Sm²⁺) and the previously ionized luminescent centres (Eu³⁺) under infrared irradiation. PACS 78.55.-m; 78.45.+h; 78.55.Et     

CaS:Eu,Sm及其在农用转光膜上的应用原理

利用稀土直接掺杂工艺合成了一种“常光充能”型电子陷获材料CaS:Eu,Sm,它不仅具有CaS:Eu无机发光材料的荧光光谱特性,而且具有红外升频转换特性,可将0.8～1.6μm的红外光直接转换为～672nm的红光、量子效率高达76%,是一种优于CaS:Eu的光转换农膜添加剂.而共掺Eu²⁺、Sm³⁺和Cu⁺的CaS荧光粉有望成为一种性能优于光转换农膜添加剂CaS:Eu²⁺,Cu⁺、可人工模拟叶绿素吸收光谱的新型农用转光膜材料.     

Luminescence properties of CaS:Ce, Sm nanophosphors

CaS:Ce, Sm nanophosphors were synthesized via solid state diffusion method. X-Ray diffraction confirmed the cubic crystalline phase of CaS:Ce, Sm nanoparticles. The particle size calculated using Debye-Scherrer formula was found to be 52 nm. The morphological investigations of the nanoparticles were made using TEM and found to have nearly spherical morphology with diameter 45-50 nm, which is in close agreement with the XRD result. The PL emission characteristics of CaS:Ce, Sm as a function of cerium and samarium concentrations have been studied and CaS:Ce_0.6Sm_0.4 system has maximum emission intensity, hence it was opted for further studies. The CaS:Ce_0.6Sm_0.4 system showed independent emission of Sm and Ce when excited at 330 and 450 nm, respectively. To study the energy transfer between cerium and samarium, the CaS:Ce_0.6Sm_0.4 was excited at wavelengths other than the excitation wavelengths of Ce (450 nm) and Sm (330 nm). The existence of Ce emission (at an excitation of 390 nm) even in the absence of Ce excitation band and Sm emission at an excitation of 405 nm, which is the excitation band of Ce, indicates the energy transfer at these two wavelengths. Thermoluminescence characteristics of ⁶⁰Co irradiated CaS:Ce_0.6Sm_0.4 have been investigated for different doses of 0.14-125 Gy. All the glow curves show a single peak at 475 K. With increasing dose, the intensity of this peak increases and a shoulder is formed on the lower temperature side at 415 K at 21 Gy of exposure. CaS:Ce_0.6Sm_0.4 shows almost linear dose dependence up to 125 Gy.     

Synthesis and Sm/Sm doping effects on photoluminescence properties of Sr4Al14O25

Complete and partial samarium reduction was achieved under strong reducing atmosphere by solid-state and combustion synthesis of Sr_3.96Sm_0.04Al₁₄O₂₅. Dependence of different fluxing agents on the formation of various strontium aluminates was examined. The samples were investigated by X-ray powder diffraction, temperature dependent luminescence decay and photoluminescence measurements. Excitation with UV radiation resulted in sharp and well resolved emission lines of samarium ions. Distinct temperature behavior for Sm²⁺ and Sm³⁺ were detected in the range of 100-500 K. Estimated emission thermal quenching values (TQ_1/2) for divalent samarium were approximately 270 K while for trivalent state around 660 K. Measured luminescence decay values of Sm²⁺ are substantially lower than for Sm³⁺,≈1.7 and ≈2.7 ms, respectively. The spectral feature of Sm²⁺ emission spectrum indicates that dopant occupies low symmetry site in Sr₄Al₁₄O₂₅ compound.     

Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

UV-induced photoluminescence and thermally stimulated luminescence of CaSO4:Eu and CaF2:Tb3+ phosphors

Ultraviolet radiation induced changes in photoluminescence (PL) and thermally stimulated luminescence (TSL) of europium activated calcium sulphate (CaSO₄:Eu³⁺, Eu²⁺) and terbium doped calcium fluoride (CaF₂:Tb³⁺) phosphors have been studied. PL measurements suggest conversion of Eu³⁺ to Eu²⁺ on 254 nm irradiation corresponding to charge transfer band of Eu³⁺ ions and reduction of Eu²⁺ ions with 365 nm illumination representing a f–d transition of Eu²⁺ ions. Similar studies carried out on CaF₂:Tb³⁺ phosphor, however, do not show any significant wavelength specific changes. The integrated TSL output appears to be rate-dependent for both phosphors. The wavelength dependent changes in TSL output observed for CaSO₄:Eu phosphor have been correlated with those obtained in PL studies. The changes in TSL and PL characteristics of CaF₂:Tb³⁺ phosphor have been explained on the basis of stabilisation of traps based on matrix specific charge similarities.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

The crystallinity and the photoluminescent properties of spray pyrolized ZnO phosphor containing Eu and Eu ions

A europium doped ZnO (ZnO:Eu) particle was directly synthesized by the spray pyrolysis method. The crystal structure of samples was designated by the europium ion and the synthesis temperature. We identified the coexistence of Eu²⁺ and Eu³⁺ ions in the as prepared ZnO, which was strongly influenced by the doping concentration and the synthesis temperature. With addition of a 0.5 mol% concentration of europium ions, only the Eu²⁺ ion existed in particles, while both Eu²⁺ and Eu³⁺ ions existed in sample using 1 mol% or higher concentration of europium ions. Changing the wavelength of the excitation source, we also found that both the blue and red luminescence can be obtained.     

The effect of europium oxide impurity on the optical and physical properties of lithium potassium borate glass

The most hosts that is utilized in scientific application is borate glass. By using melt-quenching technique, five samples of lithium potassium borate (LKB) doped with different concentration of europium oxide (Eu₂O₃) were prepared. To investigate the influence of dopant on the optical and physical characteristics of the proposed glass, two methods have been applied (XRD, PL). The amorphous nature was confirmed by X-ray diffraction (XRD). The physical parameters of the glass matrix doped by different oxidation state have been analyzed, these parameters are density, molar volume, ion concentration, inter-nuclear distance, and polaron radius. The exchange in the concentration of Eu³⁺ indicated the influence of Eu as a dopant on the photoluminescence (PL) emission of LKB glasses. The emission spectrum of LKB:Eu³⁺ show a chain of emission bands, which are attributed to ⁵ D ₀-⁷ F _r (r = 1–4) transition of Eu³⁺. The luminescence studies showed four peaks 590 (yellow), 613 (orange), 650 (red), and 698 nm (red) for all samples except sample 0, the high luminescence efficiency is in emitting orange light at 613 nm.     

Luminescence of KCaSO4Cl:X, Y (X=Eu or Ce; Y=Dy or Mn) halosulfate material

Polycrystalline KCaSO₄Cl:Eu, Dy, KCaSO₄Cl:Ce, Dy and KCaSO₄Cl:Ce, Mn phosphors prepared by a solid state diffusion method have been studied for its photoluminescence (PL) characteristics. The presence of two overlapping bands at around 400 and 450 nm in the PL emission spectra of the phosphor suggests the presence of Eu²⁺ in the host compound occupying two different lattice sites. The effects of co-doping on the photoluminescence (PL) characteristics of KCaSO₄Cl:Eu or Ce phosphors have been studied. The decrease in peak intensity of the phosphor on co-doping it with Dy gives an insight into the emission mechanism of the phosphors, which involves energy transfer from Eu²⁺→Dy³⁺, Ce³⁺→Dy³⁺ and Ce³⁺→Mn²⁺.     

Crystal growth,luminescence and scintillation properties of Eu2+:CeBr3 crystals

Eu²⁺:CeBr₃ crystals were grown by vertical Bridgman growth method and slight aliovalent doping of Eu²⁺ in the CeBr₃ crystal did not change the crystal structure. The X-ray stimulated luminescence, photoluminescence, decay kinetics and scintillation properties were investigated at room temperature. The X-ray stimulated luminescence spectra exhibited wide broad emission bands from 3.54 eV to 2.95 eV in the Eu²⁺:CeBr₃ crystal with high content of 620 ppm of Eu²⁺, which were the overlap of the emission bands ascribed to 5d → 4f transition of Ce³⁺ and 4f⁶5 d¹ → 4f⁷ transition of Eu²⁺, respectively. When the content of Eu²⁺ was decreased to 70 ppm, another emission band centered at 2.29 eV was observed. The photoluminescence spectra showed the energy transfer from Ce³⁺ to Eu²⁺. This decreased the Ce³⁺ emission intensity but enhanced the Eu²⁺ emission intensity. The photoluminescence decay time of Ce³⁺ emission decreased from 14 ns to 10 ns when the content of Eu²⁺ increased from 70 ppm to 620 ppm. The decay time of the emission of 525 nm did not change with the excitation wavelength and Eu²⁺ content, which could be assigned to the excitons that were bound on Eu²⁺ related centers. The light output of the Eu:CeBr₃ crystal under the excitation of ²⁴¹Am radioactive source was less than 20.2% of Tl:NaI crystal.     

Optical study of Sr2SnO4:Eu phosphor

This work presents the influence of europium dopant on optical properties of Sr₂SnO₄:Eu³⁺ powders fabricated by a facile low temperature method. Powders were obtained from the same amounts of Eu³⁺ doping into the different concentrations of Sr(NO₃)₂. Powders were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoluminescence (PL). SEM measurements different Eu concentrations in fabricated powders was determined to found different morphologies. XRD analysis revealed the existence of crystalline Sr₂SnO₄ in the form of tetragonal and the diffraction intensity was remarkably changed. PL studies showed a red luminescence of Sr₂SnO₄:Eu³⁺ powders. The intensity of luminescence increased with better crystallinity. This approach provides economically viable route for large-scale synthesis of this kind of nanopowders.     

Eu red long afterglow in Y2O2S:Ti, Eu phosphor through afterglow energy transfer

Eu,Ti co-doped Y₂O₂S:0.03Ti,0.03Eu phosphors and single Eu or Ti doped Y₂O₂S phosphors were prepared and their luminescent properties were investigated in detail by photoluminescence (PL) spectra, long afterglow spectra and thermoluminescence spectra measurements. The results showed that Y₂O₂S:Ti,Eu phosphors possess orange-red afterglow color with afterglow time above 5 h. The reddish afterglow color, which corresponds to a set of linear Eu³⁺ emissions at low-energy range (540-630 nm), was demonstrated to come from the energy transfer process from yellow Ti afterglow emissions, the proposed energy transfer mechanism may well explain the Eu³⁺ afterglow emission.     

Photoluminescence studies of red-emitting NaEu(WO4)2 as a near-UV or blue convertible phosphor

Sodium europium double tungstate [NaEu(WO₄)₂] phosphor was prepared by the solid-state reaction method. Its crystal structure, photoluminescence properties and thermal quenching characteristics were investigated aiming at the potential application in the field of white light-emitting diodes (LEDs). The influences of Sm doping on the photoluminescence properties of this phosphor were also studied. It is found that this phosphor can be effectively excited by 394 or 464 nm light, which nicely match the output wavelengths of near-ultraviolet (UV) or blue LED chips. Under 394 or 464 nm light excitation, this phosphor exhibits stronger emission intensity than the Y₂O₂S:Eu³⁺ or Eu²⁺-activated sulfide phosphor. The introduction of Sm³⁺ ions can broaden the excitation peaks at 394 and 464 nm of the NaEu(WO₄)₂ phosphor and significantly enhance its relative luminance under 400 and 460 nm LEDs excitation. Furthermore, the relative luminance of NaEu(WO₄)₂ phosphor shows a superior thermal stability compared with the commercially used sulfide or oxysulfide phosphor, and make it a promising red phosphor for solid-state lighting devices based on near-UV or blue LED chips.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

Luminescent features of sol–gel derived rare-earth multi-doped oxyfluoride nano-structured phosphors for white LED application

Rare-earth doped oxyfluoride 75SiO₂:25PbF₂ nano-structured phosphors for white-light-emitting diodes were synthesized by thermal treatment of precursor sol–gel derived glasses. Room temperature luminescence features of Eu³⁺, Sm³⁺, Tb³⁺, Eu³⁺/Tb³⁺, and Sm³⁺/Tb³⁺ ions incorporated into low-phonon-energy PbF₂ nanocrystals dispersed in the aluminosilicate glass matrix and excited with UV light emitting diode were investigated. The luminescence spectra exhibited strong emission signals in the red (600, 610, 625, and 646 nm), green (548 and 560 nm), and blue (485 nm) wavelength regions. White-light emission was observed in Sm/Tb and Eu/Tb double-doped activated phosphors employing UV-LED excitation at 395 nm. The dependence of the luminescence emission intensities upon annealing temperature and rare-earth concentration was also examined. The results indicated that there exist optimum annealing temperature and activator ion concentration in order to obtain intense visible emission light with high color rendering index. The study suggests that the nanocomposite phosphor based upon 75SiO₂:25PbF₂ host herein reported is a promising contender for white-light LED applications.     

Investigation of the influence of silver and tin on the luminescence of trivalent europium ions in glass

Europium-doped aluminophosphate glasses prepared by the melt-quenching technique have been studied by photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS). The effects of silver and tin doping, and of further thermal processing on Eu³⁺ ions luminescence have been assessed. For the glass system containing only europium, Eu³⁺ PL observed under UV excitation is suggested to occur through energy transfer from the excited glass host. After silver and tin doping, an enhanced UV excited Eu³⁺ PL has been indicated to occur essentially due to radiative energy transfer from isolated Ag⁺ ions and/or two fold-coordinated Sn centers. Since thermal processing of the material leads to a quenching effect on Eu³⁺ PL and Ag nanoparticles (NPs) formation due to reduction of silver ions by tin, XPS was employed in order to investigate the possibility for Eu³⁺→Eu²⁺ reduction during HT as a potential source of the PL decrease. The data points towards Ag NPs as main responsible for the observed weakening of Eu³⁺ PL.     

Understanding the role of particle size on photophysical properties of CdS:Eu nanocrystals

Here, we report the role of particle size on the photoluminescence (PL) properties of CdS:Eu³⁺ nanocrystals by steady-state and time-resolved PL spectroscopy. It is found that the average decay time 〈τ〉 of undoped CdS nanocrystals increases with increasing the size. The fast component (nanosecond) is assigned due to trapping and slow component (above 10 ns) is due to defect-related emission. The decrease of fast component from 6.6 to 1.32 ns and the slow component from 20 to 14.6 ns of CdS (host) is observed in presence of Eu ions, indicating that the energy transfer occurs from CdS nanoparticles to Eu³⁺ ions. The decay time of Eu³⁺ in CdS shows two decay components (microsecond scale) and we believe that the fast component is attributed to surface-bound Eu³⁺ ions and slow component is due to lattice-bound Eu³⁺ ions. Analysis suggests that PL efficiency of Eu³⁺ ions depends on size of nanoparticles.     

Microstructural and optical properties of europium-doped zinc oxide nanowires

Single-crystal Eu³⁺-doped wurtzite ZnO micro- and nanowires were synthesized by chemical vapor deposition. The nanostructures grew via a self-catalytic mechanism on the walls of an alumina boat. The structure and properties of the doped ZnO were characterized using X-ray diffraction, energy-dispersive X-ray spectroscopy, scanning and transmission electron microscopy, and photoluminescence (PL) methods. A 10-min synthesis yielded vertically grown nanowires of 50–400 nm in diameter and several micrometers long. The nanowires grew along the ±[0001] direction. The Eu³⁺ concentration in the nanowires was 0.8 at.%. The crystal structure and microstructure of were compared for Eu³⁺-doped and undoped ZnO. PL spectra showed a red shift in emission for Eu³⁺-doped (2.02 eV) compared to undoped ZnO nanowires (2.37 eV) due to Eu³⁺ intraionic transitions. Diffuse reflectance spectra revealed widening of the optical bandgap by 0.12 eV for Eu³⁺-doped compared to undoped ZnO to yield a value of 3.31 eV. Fourier-transform infrared spectra confirmed the presence of europium in the ZnO nanowires.